EP1698663B1 - (meth)acrylharzzusammensetzung - Google Patents

(meth)acrylharzzusammensetzung Download PDF

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Publication number
EP1698663B1
EP1698663B1 EP04729982A EP04729982A EP1698663B1 EP 1698663 B1 EP1698663 B1 EP 1698663B1 EP 04729982 A EP04729982 A EP 04729982A EP 04729982 A EP04729982 A EP 04729982A EP 1698663 B1 EP1698663 B1 EP 1698663B1
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meth
weight
acrylic resin
resin composition
monomer
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French (fr)
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EP1698663A4 (de
EP1698663A1 (de
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Hideyuki Sakamoto
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Kaneka Corp
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Kaneka Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a (meth)acrylic resin composition, in which thermal degradation when processing is inhibited and discoloring hardly occurs, and a capstock and extrusion-molded article comprising the (meth)acrylic resin composition.
  • (Meth)acrylic resin has conventionally been used as substitute material for glass due to water-clear appearance characteristic of (meth)acrylic resin. Utilizing its excellent weather resistance, (meth)acrylic resin is also used as a capstock, which covers the surface of materials used outdoors.
  • (Meth)acrylic resin is prepared by radical polymerization such as bulk polymerization, suspension polymerization and emulsion polymerization and of these, bulk polymerization is most widely employed, in that the amount of impurities is small.
  • the final form of the (meth)acrylic resin product is pellets.
  • the ingredients added when forming the composition such as an impact modifier and a processing aid are in the form of powder, the pellets and the powder separate when compounding, transporting and extrusion molding and mixing and dispersion of the constituent elements may become inhomogeneous.
  • the amount of the dispersion stabilizer is decreased, because the dispersion stabilization of monomer and polymer drops decrease along with decrease in concentration, the monomer and polymer drops adhere together and consequently, polymer particles with a wide particle distribution are produced. Also, when the balance of conditions is lost, the entire polymerization system may agglomerate. Therefore, the problem of thermal degradation when processing makes selecting the type of dispersion stabilizer and adjusting the concentration difficult, in terms of stable production and particle size control.
  • US 6,001,913 discloses latex compositions containing ethylenically unsaturated esters of long-chain alkenols having low volatile organic content and low odor.
  • WO 02/28944 discloses a non-extractable polymeric metal salt useful in catalyzing oxygen scavenging.
  • EP 1 178 079 A1 discloses a rubber-reinforced transparent resin composition and a method of producing the same.
  • US 2002/0013410 A1 discloses an impact modifier having improved blocking resistance.
  • US 5,741,854 discloses vinyl aromatic resin compositions containing a fluoroolefin polymer and a metal salt or ester or a fatty acid.
  • US 4,329,276 discloses a molding blend component consisting of an acrylic polymer, selected ethylene terpolymers and carbon black which is said to be useful for the molding of polyvinyl chloride.
  • JP 2002-241572 A discloses an acrylic resin composition comprising an agent for improving impact resistance in a multilayer structure and an acrylic resin containing a homopolymer or copolymer of methyl methacrylate.
  • the object of the present invention is to provide a (meth)acrylic resin composition, in which thermal degradation when processing is inhibited and discoloring hardly occurs, which could not be obtained in the conventional (meth)acrylic resin composition containing (meth)acrylic resin prepared by suspension polymerization.
  • (meth)acryl refers to acryl and/or methacryl
  • the present invention relates to a (meth)acrylic resin composition
  • a (meth)acrylic resin composition comprising 100 parts by weight of a methyl methacrylate polymer obtainable by suspension polymerizing 50 to 100 % by weight of methyl methacrylate and 50 to 0 % by weight of a monomer copolymerizable therewith, 1 to 200 parts by weight of a copolymer having a multi-layer structure, a partially saponified polyvinyl alcohol as a dispersion stabilizer for the suspension polymerization and 0.02 to 10 parts by weight of a fatty acid metallic salt; wherein the copolymer having a multi-layer structure is obtainable by polymerizing a monomer or monomer mixture containing at least alkyl (meth)acrylate ester in the presence of an acrylic crosslinked rubber.
  • the content of the copolymer having a multi-layer structure is preferably 30 to 160 parts by weight.
  • the content of the fatty acid metallic salt is preferably 0.1 to 5 parts by weight.
  • the fatty acid of the fatty acid metallic salt preferably has 8 to 20 carbon atoms.
  • the metal of the fatty acid metallic salt is preferably an alkali metal or an alkali earth metal.
  • the ionic valency of the metal of the fatty acid metallic salt is preferably 2.
  • the fatty acid metallic salt is preferably calcium stearate.
  • the copolymer having a multi-layer structure is preferably a copolymer having a three-layer structure, which is obtainable by polymerizing a monomer or monomer mixture containing at least alkyl (meth)acrylate ester in the presence of a two-layer polymer, which is obtainable by polymerizing a monomer mixture containing at least alkyl acrylate ester and a crosslinkable monomer in the presence of a polymer comprising a monomer mixture containing at least methyl methacrylate and a crosslinkable monomer.
  • the present invention also relates to capstock comprising the (meth)acrylic resin composition.
  • the present invention also relates to an extrusion-molded article obtainable by using the capstock.
  • the (meth)acrylic resin composition of the present invention contains 100 parts by weight of a methyl methacrylate polymer comprising 50 to 100 % by weight of methyl methacrylate and 50 to 0 % by weight of a monomer copolymerizable therewith, 1 to 200 parts by weight of a copolymer having a multi-layer structure, a partially saponified polyvinyl alcohol as a dispersion stabilizer for the suspension polymerization and 0.02 to 10 parts by weight of a fatty acid metallic salt; wherein the copolymer having a multi-layer structure is obtainable by polymerizing a monomer or monomer mixture containing at least alkyl (meth)acrylate ester in the presence of an acrylic crosslinked rubber.
  • Examples of the monomer copolymerizable with methyl methacrylate are vinyl arenes such as styrene, ⁇ -methylstyrene, monochlorostyrene and dichlorostyrene; vinyl carboxylic acids such as acrylic acid and methacrylic acid and esters thereof; vinyl cyans such as acrylonitrile and methacrylonitrile; halogenated vinyls such as vinyl chloride, vinyl bromide and chloroprene; vinyl acetate; alkenes such as ethylene, propylene, butylene, butadiene and isobutylene; halogenated alkenes; and multifunctional monomers such as allyl methacrylate, diallyl phthalate, triallyl cyanurate, monoethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, divinylbenzene and glycidyl methacrylate.
  • vinyl arenes such as styrene, ⁇ -methylstyrene
  • the (meth)acrylic resin composition of the present invention is used as capstock resin for covering the surface of materials used outdoors by utilizing excellent weather resistance of polymethyl methacrylate
  • a (meth)acrylic ester monomer with an alkyl group having 1 to 12 carbon atoms, which does not impair weather resistance phenyl (meth)acrylate and benzyl (meth)acrylate are preferably used as the copolymerizable monomer.
  • Examples of the (meth)acrylic ester with an alkyl having 1 to 12 carbon atoms are methyl acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, and isobornyl (meth)acrylate.
  • the methyl methacrylate polymer contains 50 to 100 % by weight, preferably 50 to 99.9 % by weight, more preferably 70 to 98 % by weight of methyl methacrylate and 50 to 0 % by weight, preferably 50 to 0.1 % by weight, more preferably 30 to 2 % by weight of a monomer copolymerizable with methyl methacrylate.
  • content of methyl methacrylate is less than 50 % by weight, appearance, weather resistance and heat resistance, which are characteristic of (meth)acrylic resin, tend to decrease.
  • the methyl methacrylate polymer is obtainable by suspension polymerizing the mixture of methyl methacrylate and a monomer copolymerizable therewith.
  • the average particle size of the polymer particles obtained by suspension polymerization is not particularly limited, but is preferably 50 to 500 ⁇ m as obtained in the usual suspension polymerization process. More preferably, the average particle size is 50 to 250 ⁇ m, from the viewpoint that in the case that polymer particles are compounded with ingredients added when processing such as a impact modifier and a processing aid, separation does not occur when transporting and extrusion molding and mixing and dispersion do not become inhomogeneous.
  • partially saponified polyvinyl alcohol which is usually used in suspension polymerization of a methyl methacrylate polymer
  • the average particle size of the suspension polymer particles can be kept to 50 to 250 ⁇ m, which is preferable when compounding with ingredients added when processing such as a impact modifier and a processing aid, and stable polymerization properties can be obtained.
  • peroxides such as benzoyl peroxide and lauroyl peroxide and azo compounds such as azo bis isobutyronitrile
  • azo compounds such as azo bis isobutyronitrile
  • a chain transfer agent can be used.
  • alkyl mercaptan having 2 to 18 carbon atoms thioglycollic acid ester and mercaptic acids such as ⁇ -mercapto propionic acid and aromatic mercaptan including benzyl mercaptan, thiophenol, thiocresol and thionaphthol can be used.
  • alkyl mercaptan having 4 to 12 carbon atoms is preferable.
  • all known methods can be used, such as the method of suspending the monomer or monomer mixture in water and then conducting the polymerization reaction and the method of conducting the polymerization reaction by suspending part of the monomer or monomer mixture in water to start the polymerization reaction and then, as the polymerization reaction progresses, adding the remaining water suspension of the monomer or monomer mixture to the polymerization reaction bath either divided into one or more steps or continuously.
  • the method for adding the polymerization initiator and the chain transfer agent is not particularly limited, but the method of dissolving both the polymerization initiator and the chain transfer agent in the monomer, suspending the monomer in water and then conducting the polymerization reaction is most preferable.
  • the time required for polymerization differs according to the type and amount of the polymerization initiator and the polymerization temperature but is usually 1 to 24 hours.
  • components usually added when mold processing rigid plastic, such as a plasticizer, lubricant, stabilizer and UV ray absorbent can be added to the monomer.
  • Examples of the method for recovering the suspension polymer of the methyl methacrylate polymer are the known methods of recovering by washing and drying and recovering by adding a polymer prepared by emulsion polymerization and an electrolyte to the suspension polymer particles while stirring.
  • the polymer particles recovered by either method can suitably be used.
  • the copolymer having a multi-layer structure is an impact modifier essential for providing excellent impact resistance, which is necessary when using the (meth)acrylic resin composition of the present invention as capstock resin.
  • 1 to 200 parts by weight, preferably 30 to 160 parts by weight of the copolymer is compounded based on 100 parts by weight of the methyl methacrylate polymer.
  • the amount is too small, sufficient impact strength cannot be obtained and when the amount is too large, the pressure of melted resin and torque when processing become high and processing becomes difficult.
  • the copolymer having a multi-layer structure preferably has a two to four layer structure, more preferably a three to four layer structure.
  • a copolymer obtainable by polymerizing a monomer or monomer mixture containing at least alkyl (meth)acrylate ester and when necessary, a monomer copolymerizable with (meth)acrylic ester, such as an aromatic vinyl monomer, in the presence of acrylic crosslished rubber is used from the viewpoints that compatibility with (meth)acrylic resin is favorable and strength is significantly improved.
  • Various kinds of such copolymers having a multi-layer structure are known and for example, the multi-structural body disclosed in JP-B-55-27576 can be used.
  • a copolymer having a three-layer structure which is obtainable by polymerizing a monomer or monomer mixture containing (meth)acrylic ester and when necessary, a monomer copolymerizable therewith in the presence of a two-layer polymer, which is obtainable by polymerizing a monomer mixture containing alkyl acrylate ester, a crosslinkable monomer and when necessary, a monomer copolymerizable with alkyl acrylate ester in the presence of a polymer comprising a monomer mixture containing methyl methacrylate, a crosslinkable monomer and when necessary, a monomer copolymerizable with methyl methacrylate and (2) a copolymer having a two-layer structure, which is obtainable by polymerizing a monomer or monomer mixture containing (meth)acrylic ester and when necessary, a monomer copolymerizable therewith in the presence of an acrylic crosslinked rubber can suitably be used.
  • examples of the monomer copolymerizable with methyl methacrylate, which forms the inner most layer are alkyl methacrylate esters having 2 to 8 carbon atoms such as ethyl methacrylate, propyl methacrylate and n-butyl methacrylate; acrylic esters having 1 to 12 carbon atoms such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate and 2-ethylhexyl acrylate; (meth)acrylic esters having a cyclic compound in the ester group such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate and benzyl (meth)acrylate; aromatic vinyls such as styrene, ⁇ -methylstyrene,
  • crosslinkable monomer allyl methacrylate, allyl acrylate, divinyl benzene, diallyl maleate, diallyl fumarate, diallyl itaconate, monoallyl maleate, monoallyl fumarate and butadiene can be used.
  • the weight ratio of the methyl methacrylate, the copolymerizable monomer and the crosslinkable monomer in the monomer mixture which forms the innermost layer is preferably 1 to 99.99:0 to 98.99:0.01 to 5, more preferably 50 to 99.9:0 to 49.9:0.1 to 3. When the proportion is out of this range, impact resistance, surface hardness and heat resistance tend to decrease and weather resistance tends to become poor.
  • alkyl acrylate ester which forms the middle layer
  • alkyl acrylate esters with an alkyl group having 1 to 12 carbon atoms such as ethyl acrylate, n-butyl acrylate, n-octyl acrylate and 2-ethylhexyl acrylate.
  • Examples of the monomer copolymerizable with alkyl acrylate ester are alkyl methacrylate esters having 1 to 8 carbon atoms such as ethyl methacrylate, propyl methacrylate and n-butyl methacrylate; (meth)acrylic esters having a cyclic compound in the ester group such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate and benzyl (meth)acrylate; aromatic vinyls such as styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and chlorostyrene; acrylonitrile; (meth)acrylic acid and hydroxyethyl methacrylate.
  • alkyl methacrylate esters having 1 to 8 carbon atoms such as ethyl methacrylate, prop
  • crosslinkable monomer examples are the same monomers as those described above for the innermost layer.
  • the weight ratio of the alkyl acrylate ester, the copolymerizable monomer and the crosslinkable monomer in the monomer mixture which forms the middle layer is preferably 50 to 99.99:0 to 49.99:0.01 to 5, more preferably 70 to 99.9:0 to 29.9:0.1 to 3. When the proportion is out of this range, impact resistance tends to decrease and weather resistance tends to become poor.
  • Examples of the (meth)acrylic ester which forms the outermost layer are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)arylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate and benzyl (meth)acrylate.
  • Examples of the monomer copolymerizable with (meth)acrylic ester are aromatic vinyl monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene and chlorostyrene; acrylonitrile; (meth)acrylic acid and hydroxyethyl methacrylate.
  • the weight ratio of the (meth)acrylic ester and the copolymerizable monomer in the monomer mixture which forms the outermost layer is preferably 50 to 100:0 to 50, more preferably 70 to 95:5 to 25. When the proportion is out of this range, impact resistance tends to decrease, weather resistance tends to become poor and the surface of the molded article tends to become rough.
  • the weight ratio of the monomer forming the innermost layer, the monomer forming the middle layer and the monomer forming the outermost layer is preferably 3 to 50:10 to 92:5 to 87, more preferably 10 to 40:20 to 75:10 to 70.
  • the proportion is out of this range, impact resistance tends to decrease, weather resistance tends to become poor and the surface of the molded article tends to become rough.
  • the acrylic crosslinked rubber can be formed by using the same monomers as the alkyl acrylate ester and the crosslinkable monomer used when forming the middle layer of the copolymer having a three-layer structure (1). Also, when necessary, a monomer copolymerizable with alkyl acrylate ester can be used.
  • the outer layer is formed by polymerizing in the same manner the same monomers as the (meth)acrylic ester and the monomer copolymerizable therewith used when forming the outermost layer of the copolymer having a three-layer structure (1).
  • the weight ratio of the acrylic crosslinked rubber and the monomer forming the outer layer is preferably 50 to 95:50 to 5, more preferably 70 to 90:30 to 10. When the proportion is out of this range, impact resistance and dispersability tend to decrease.
  • the polymerization method for obtaining a copolymer having such a multi-layer structure is not particularly limited but in actual use, a known emulsion polymerization method is convenient.
  • fatty acid metallic salt used in the present invention metallic salt of saturated fatty acid or unsaturated fatty acid can be used.
  • fatty acid metallic salt of fatty acid having 8 to 20 carbon atoms is suitable.
  • the metal of the fatty acid metallic salt is preferably an alkali metal or an alkali earth metal. Examples are calcium stearate, magnesium stearate, calcium laurate, sodium palmitate, potassium palmitate, sodium oleate, lithium stearate, strontium stearate, barium stearate, cadmium stearate, cadmium laurate, zinc stearate and zinc laurate.
  • calcium stearate is particularly preferable.
  • the ionic valency of the metal of the fatty acid metallic salt is preferably 2.
  • the partially saponified polyvinyl alcohol which is used as a dispersion stabilizer in suspension polymerization when obtaining the methyl methacrylate polymer used in the present invention
  • the partially saponified polyvinyl alcohol which is used as a dispersion stabilizer in suspension polymerization when obtaining the methyl methacrylate polymer used in the present invention
  • the partially saponified polyvinyl alcohol is known to relatively easily cause thermal degradation when processing near the molding temperature and to cause decoloration the lower the saponification degree.
  • decoloration is small in comparison to partially saponified polyvinyl alcohol, other dispersion stabilizers such as methyl cellulose also cause decoloration under severe processing conditions.
  • thermal degradation which occurs when processing the (meth)acrylic resin composition of the present invention containing the methyl methacrylate polymer obtained by suspension polymerization, can be significantly inhibited.
  • the (meth)acrylic resin composition of the present invention 0.02 to 10 parts by weight, preferably 0.1 to 5 parts by weight, of a fatty acid metallic salt is added based on 100 parts by weight of the methyl methacrylate polymer.
  • 0.02 to 10 parts by weight preferably 0.1 to 5 parts by weight, of a fatty acid metallic salt is added based on 100 parts by weight of the methyl methacrylate polymer.
  • the amount is less than 0.02 part by weight, the effect of inhibiting thermal degradation when processing is small and when the amount is more than 10 parts by weight, plate-out objects are produced and problems may occur, such as staining of the cooling die when molding.
  • the method for mixing the methyl methacrylate polymer, the copolymer having a multi-layer structure and the fatty acid metallic salt is not particularly limited.
  • the methyl methacrylate polymer, the copolymer having a multi-layer structure and the fatty acid metallic salt can be mixed together as powder, can be mixed in latex of the copolymer having a multi-layer structure obtained by polymerization or can be added when recovering suspension polymer particles.
  • the (meth)acrylic resin composition of the present invention is suitably used in an extrusion molded article such as a capstock.
  • additives such as a deglossing agent prepared by the known method of micro suspension polymerization, an antioxidant, a photostabilizer, a lubricant and pigment may be added when necessary.
  • a deglossing agent prepared by the known method
  • examples of the inorganic deglossing agent are calcium carbonate, barium sulfate, aluminum hydroxide, talc, mica, glass and silica and examples of the organic deglossing agent are a styrene crosslinked polymer and an acrylic crosslinked polymer.
  • an organic, deglossing agent is preferable and a deglossing agent having a core/shell structure, in which the core layer is a rubbery alkyl acrylate polymer having an average particle size of 2 to 20 ⁇ m and the shell layer is compatible with a matrix polymer, described in for example JP-A-10-87710 , JP-A-10-120714 and JP-A-10-120715 , is more preferable.
  • the acrylic resin composition of the present invention is hardly discolored, as thermal degradation when processing is inhibited.
  • a molded article having a b value which represents the degree of yellowing measured using a color-difference meter, of 1 to 20, more preferably 1 to 10, can be obtained.
  • the b value can be measured for example according to JIS K7105.
  • a reaction vessel equipped with a stirrer was charged with 220 parts of deionized water and 15 parts by weight of a 3 % aqueous solution of polyvinyl alcohol (GH-20: available from The Nippon Synthetic Chemical Industry Co., Ltd.) and the inside of the reaction vessel was substituted with nitrogen. Then, a monomer mixture comprising 90 parts by weight of methyl methacrylate, in which 0.5 part by weight of lauroyl peroxide and 0.5 part by weight of benzoyl peroxide are dissolved, and 10 parts by weight of butyl acrylate was added thereto and the rotational speed of the stirrer was adjusted so that the dispersion particle size of the monomer became approximately 250 ⁇ m.
  • GH-20 polyvinyl alcohol
  • a glass reaction vessel was charged with a mixture of the following composition and the temperature was raised to 80°C while stirring in a nitrogen current. Then, 25 % of the mixture of the innermost layer components comprising 24 parts by weight of methyl methacrylate, 1 part by weight of butyl acrylate, 0.1 part by weight of allyl methacrylate and 0.1 part by weight of t-butyl hydroperoxide was added at once and polymerization was conducted for 45 minutes.
  • the average particle size of the polymer particles in the latex of the obtained crosslinked methacrylic polymer was 1600 ⁇ (found using light scattering of wavelength of 546 nm) and the polymerization conversion ratio ((amount of polymers produced/amount of monomers charged) x 100) was 98 %.
  • a latex of the crosslinked methacrylic polymer obtained in (a) was maintained at 80°C in a nitrogen current. After 0.1 part by weight of potassium persulfate was added, a monomer mixture comprising 41 parts by weight of n-butyl acrylate, 9 parts by weight of styrene and 1 part by weight of allyl methacrylate was continuously added over 5 hours. During this time, 0.1 part by weight of potassium oleate was added divided into three times. After adding the monomer mixture, 0.05 part by weight of potassium persulfate was added and the temperature was maintained for 2 hours to complete polymerization. The average particle size of the obtained polymer was 2300 ⁇ and the polymerization conversion ratio was 99 %.
  • a latex of the rubbery polymer obtained in (b) was maintained at 80°C. After 0.02 part by weight of potassium persulfate was added, a mixture comprising 24 parts by weight of methyl methacrylate, 1 part by weight of n-butyl acrylate and 0.1 part by weight of t-dodecyl mercaptan was continuously added over 1 hour. After adding the monomer mixture, the temperature was maintained for 1 hour to obtain a latex of a three-layer structure graft copolymer. The average particle size of the obtained three-layer structure graft copolymer 2530 ⁇ and the polymerization conversion ratio was 99 %. The latex of the obtained three-layer structure graft copolymer was salted-out and coagulated, thermally treated and dried by a known method to obtain a copolymer having a three-layer structure in the form of white powder (impact modifier).
  • SC-100 calcium stearate, available from Sakai Chemical Industry Co., Ltd.
  • SC-100 a fatty acid metallic salt
  • a glass reaction vessel was charged with the following mixture and heated to 50°C while stirring in a nitrogen current. Then, a monomer mixture comprising 100 parts by weight of n-butyl acrylate, 1 part by weight of allyl methacrylate and 0.1 part by weight of cumene hydroperoxide was dropped over 4 hours. Along with adding the monomer mixture, 2 parts by weight of a 5 % aqueous solution containing potassium stearate was continuously added over 4 hours. After adding, stirring was continued for 5 hours to complete polymerization. The polymerization conversion ratio was 97 % and the average particle size of the obtained polymer was 700 ⁇ .
  • a glass reaction vessel was charged with 75 parts by weight (as solid content) of a latex of the rubbery polymer obtained in (a), 0.05 part by weight of formaldehyde sodium sulfoxylate, 0.01 part by weight of ethylenediamine sodium tetraacetate and 0.005 part by weight ferrous sulfate. Then, the aqueous dispersion was heated and stirred at 50°C in a nitrogen current. Thereafter, 20 parts by weight of methyl methacrylate and 5 parts by weight of butyl methacrylate, which are the monomer components for graft polymerization, and 0.05 part by weight of cumene hydroperoxide, which is the polymerization initiator, were continuously added over 1 hour.
  • the latex of the obtained graft copolymer having a two-layer structure was salted-out and coagulated, thermally treated and dried by a known method to obtain a copolymer having a two-layer structure in the form of white powder (impact modifier).
  • the average particle size of the graft copolymer having a two-layer structure was 1900 ⁇ .
  • the molded article for evaluation was obtained by molding in the same manner as in Example 1, except that the copolymer having a two-layer structure was used instead of the copolymer having a three-layer structure of Example 1.
  • the results of measuring the degree of yellowing are shown in Table 1.
  • the molded article for evaluation was obtained in the same manner as in Example 1, except that the fatty acid metallic salt was not used.
  • the results of measuring the degree of yellowing are shown in Table 1.
  • a fatty acid metallic salt particularly a specific fatty acid metallic salt
  • discoloring due to thermal degradation when processing which was a problem of the conventional (meth)acrylic resin composition obtained by suspension polymerization, can be inhibited.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Claims (10)

  1. (Meth)acrylharzzusammensetzung, umfassend 100 Gewichtsteile eines Methylmethacrylatpolymers, erhältlich durch Suspensionspolymerisation von 50 bis 100 Gewichtsprozent eines Methylmethacrylats mit 50 bis 0 Gewichtsprozent eines damit copolymerisierbaren Monomers, 1 bis 200 Gewichtsteile eines Copolymers mit mehrschichtiger Struktur, einen teilweise verseiften Polyvinylalkohol als Dispersionsstabilisator für die Suspensionspolymerisation und 0,02 bis 10 Gewichtsteile eines Fettsäuremetallsalzes; wobei das Copolymer mit der mehrschichtigen Struktur erhältlich ist durch Polymerisieren eines Monomers oder Monomergemisches, enthaltend mindestens Alkyl(meth)acrylatester in Gegenwart eines vernetzten Acrylkautschuks.
  2. (Meth)acrylharzzusammensetzung nach Anspruch 1, wobei der Gehalt des Copolymers mit mehrschichtiger Struktur 30 bis 160 Gewichtsteile beträgt.
  3. (Meth)acrylharzzusammensetzung nach Anspruch 1, wobei der Gehalt des Fettsäuremetallsalzes 0,1 bis 5 Gewichtsteile beträgt.
  4. (Meth)acrylharzzusammensetzung nach Anspruch 1, wobei die Fettsäure des Fettsäuremetallsalzes 8 bis 20 Kohlenstoffatome aufweist.
  5. (Meth)acrylharzzusammensetzung nach Anspruch 1, wobei das Metall des Fettsäuremetallsalzes ein Alkalimetall oder ein Erdalkalimetall ist.
  6. (Meth)acrylharzzusammensetzung nach Anspruch 1, wobei die Ionenwertigkeit des Metalls des Fettsäuremetallsalzes 2 ist.
  7. (Meth)acrylharzzusammensetzung nach Anspruch 1, wobei das Fettsäuremetallsalz ein Calciumstearat ist.
  8. (Meth)acrylharzzusammensetzung nach Anspruch 1, wobei das Copolymer mit mehrschichtiger Struktur ein Copolymer mit dreischichtiger Struktur ist, erhältlich durch Polymerisation eines Monomers oder eines Monomergemisches, enthaltend mindestens Alkyl(meth)acrylatester in Gegenwart eines zweischichtigen Polymers, erhältlich durch Polymerisation eines Monomergemisches, enthaltend mindestens Alkylacrylatester und ein vernetzbares Monomer in Gegenwart eines Polymers, umfassend ein Monomergemisch, enthaltend mindestens Methylmethacrylat und ein vernetzbares Monomer.
  9. Capstock, umfassend die (Meth)acrylharzzusammensetzung nach Anspruch 1, 2, 3, 4, 5, 6, 7 oder 8.
  10. Extrusionsgeformter Gegenstand, erhältlich durch Verwendung des Capstocks nach Anspruch 9.
EP04729982A 2003-12-26 2004-04-28 (meth)acrylharzzusammensetzung Expired - Lifetime EP1698663B1 (de)

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JP2003434890A JP5133493B2 (ja) 2003-12-26 2003-12-26 （メタ）アクリル樹脂組成物
PCT/JP2004/005662 WO2005066267A1 (ja) 2003-12-26 2004-04-28 （メタ）アクリル樹脂組成物

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TWI287025B (en) 2004-08-31 2007-09-21 Nippon Catalytic Chem Ind Optical sheet form thermoplastic resin molded product
DE102007009268B4 (de) * 2006-03-01 2014-09-25 Nippon Shokubai Co., Ltd. Thermoplastische Harzzusammensetzung und Herstellungsverfahren für diese
EP2189502B1 (de) * 2007-09-11 2013-05-15 Kaneka Corporation Flüssige harzzusammensetzung und gehärtetes produkt unter verwendung der flüssigen harzzusammensetzung
JP2012052054A (ja) * 2010-09-03 2012-03-15 Kaneka Corp 樹脂組成物及びその成形体
EP2662391B1 (de) * 2011-01-06 2018-11-21 Kaneka Corporation Herstellungsverfahren für methyl-methacrylat-polymer
JP5726053B2 (ja) * 2011-11-25 2015-05-27 Ｊｘ日鉱日石エネルギー株式会社 光学フィルム用メタクリル系樹脂の製造方法

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US3793402A (en) * 1971-11-05 1974-02-19 F Owens Low haze impact resistant compositions containing a multi-stage,sequentially produced polymer
US4329276A (en) * 1981-03-11 1982-05-11 E. I. Du Pont De Nemours And Company Molding components
US5741854A (en) * 1994-11-21 1998-04-21 General Electric Company Vinyl aromatic resin compositions containing a fluoro olefin polymer and a metal salt or ester or a fatty acid
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JP3945861B2 (ja) * 1997-07-29 2007-07-18 三菱レイヨン株式会社 熱可塑性樹脂組成物
JP2002053729A (ja) * 2000-08-04 2002-02-19 Kanegafuchi Chem Ind Co Ltd 耐ブロッキング性の改良された耐衝撃性改良剤
MY124925A (en) * 2000-07-26 2006-07-31 Toray Industries Rubber-reinforced styrene transparent resin composition and method of producing the same
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JP3901534B2 (ja) * 2001-10-11 2007-04-04 株式会社クレハ 制電性樹脂組成物
JP4060064B2 (ja) * 2001-11-26 2008-03-12 三菱レイヨン株式会社 グラフト共重合体およびそれを含む熱可塑性樹脂組成物
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JP2003327777A (ja) * 2002-05-10 2003-11-19 Mitsubishi Rayon Co Ltd 熱可塑性樹脂組成物

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CA2540882A1 (en) 2005-07-21
CN100436534C (zh) 2008-11-26
KR20060126743A (ko) 2006-12-08
CN1871296A (zh) 2006-11-29
JP5133493B2 (ja) 2013-01-30
ATE407178T1 (de) 2008-09-15
WO2005066267A1 (ja) 2005-07-21
EP1698663A4 (de) 2007-02-21
JP2005194298A (ja) 2005-07-21
EP1698663A1 (de) 2006-09-06

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